CN103553016A - Preparation method of lithium iron phosphate with polyphosphoric acid and ammonium dihydrogen phosphate as composite phosphorus sources - Google Patents
Preparation method of lithium iron phosphate with polyphosphoric acid and ammonium dihydrogen phosphate as composite phosphorus sources Download PDFInfo
- Publication number
- CN103553016A CN103553016A CN201310511418.4A CN201310511418A CN103553016A CN 103553016 A CN103553016 A CN 103553016A CN 201310511418 A CN201310511418 A CN 201310511418A CN 103553016 A CN103553016 A CN 103553016A
- Authority
- CN
- China
- Prior art keywords
- lithium
- polyphosphoric acid
- phosphate
- source
- dihydrogen phosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a method for synthesizing lithium iron phosphate by taking polyphosphoric acid and ammonium dihydrogen phosphate as composite phosphorus sources. In a pre-ball-milling step, the polyphosphoric acid and the ammonium dihydrogen phosphate are selected as the composite phosphorus sources; when the polyphosphoric acid and the ammonium dihydrogen phosphate are mixed with a lithium source, the ammonium dihydrogen phosphate is likely to react with the lithium source to produce lithium dihydrogen phosphate with byproducts of water and ammonia gas; the polyphosphoric acid is hydrolyzed in water to produce orthophosphoric acid; the ammonia gas can be further absorbed by the orthophosphoric acid to obtain the ammonium dihydrogen phosphate and thus also participates in the reaction of the lithium source, so that the purpose of reducing the byproducts of water and ammonia gas in the mixing system can be achieved; meanwhile, the ammonia salt and the lithium source are previously ball-milled, so that the reaction of the ammonia salt and the lithium source is sufficient, and the full production of the lithium dihydrogen phosphate and the synthesis of the pure-phase lithium iron phosphate are facilitated. The method is easy to operate, causes little pollution to the environment and can effectively improve the electrochemical performance of the lithium iron phosphate material.
Description
Technical field
The present invention relates to method for preparing lithium iron phosphate material, particularly relate to a kind of method that polyphosphoric acid and primary ammonium phosphate be compound phosphorus source synthesizing iron lithium phosphate material of take.
Background technology
Goodenough equals 1997 by exploring M
2(XO
4)
3(X=W, S, As, P, MO, M=V, Ti, Nb, Fe) serial magnesium-yttrium-transition metal polyanionic compound, the olivine structural of finding iron lithium phosphate is very stable, in charge and discharge process, it is very little that lithium ion embeds/deviate from the volume change that the lattice of iron lithium phosphate produces, so propose first olivine structure lithium iron phosphate, has charging and discharging capabilities.Lithium iron phosphate positive material theoretical capacity 170mAh/g, discharge platform is stable, reach 3.4V, there is high security, high efficiency for charge-discharge, long cycle life, specific storage is high, overcharging resisting is electric and overdischarge ability strong, high temperature capacity is high, environmental protection and lower-price characteristic, is considered to a kind of very promising anode material for lithium-ion batteries.
The preparation method of iron lithium phosphate has high temperature solid-state method, liquid-phase precipitation method, hydrothermal method, sol-gel method, microwave process for synthesizing and oxidation reduction process etc.Wherein, high temperature solid-state method, because technique is simple, is easily realized industrialization, is the synthetic method that current domestic and international most of producer realizes LiFePO 4 material volume production.
It is raw material that general high temperature solid-state method be take Ferrox or Iron diacetate, primary ammonium phosphate or Secondary ammonium phosphate, sucrose and Quilonum Retard, after even by chemical ratios ground and mixed, in nitrogen atmosphere, in 200-650 ℃ of presintering, and then 600-800 ℃ of sintering prepared iron lithium phosphate.There is following defect in above-mentioned technique: 1, during batch mixing ammonium salt can with lithium source water generation reaction, and monometallic solubleness in water that organic carbon source, Ferrox and reaction generate differs larger, in drying process subsequently, easily produce segregation, the iron lithium phosphate impurity phase that causes sintering to be prepared is more, affects the performance of its electrical property; 2, batch mixing and sintering process can produce a large amount of ammonias, and strong to human body pungency and corrodibility, environmental pollution is larger.
Summary of the invention
The technical problem to be solved in the present invention is that prior art scheme is improved and improved, a kind of method that polyphosphoric acid and primary ammonium phosphate be compound phosphorus source synthesizing iron lithium phosphate material of take is provided, in minimizing technological process, the generation of water byproduct and ammonia, reaches the object of improving material electrochemical performance and alleviating production process environmental pollution.For this reason, the present invention is by the following technical solutions:
Take the method that polyphosphoric acid and primary ammonium phosphate be compound phosphorus source synthesizing iron lithium phosphate material, it is characterized in that it comprises the following steps:
1) pre-ball milling step, is placed in ball grinder by polyphosphoric acid, primary ammonium phosphate and Li source compound, carries out wet ball grinding, and Ball-milling Time is 0.5-2h, makes monometallic complete reaction generation in advance; Wherein, polyphosphoric acid is pressed P
2o
5timing, the mol ratio of lithium and phosphorus is 1:1, the proportional range that the phosphorus mole number that primary ammonium phosphate provides accounts for the phosphorus mole number that compound phosphorus source provides is 10%-90%;
2) secondary ball milling step, in reaction in advance, generate in the ball grinder of monometallic, add in proportion Fe source compound and organic carbon source, continue ball milling 2-5h, then at 70 ℃, dry, wherein the mol ratio of lithium, iron and phosphate radical is 1:1:1, and the quality of organic carbon source is about the 7%-12% of iron lithium phosphate quality;
3) sintering step; the crushing material of drying is placed in atmosphere furnace; under non-oxidizing atmosphere protection; temperature rise rate with 2-5 ℃/min rises to 350-500 ℃ from room temperature; insulation 2-4h; with the temperature rise rate of 2-5 ℃/min, rise to roasting at 700-800 ℃ again, roasting time is 6-10h, thereby prepares LiFePO 4 material.
As the further of technique scheme improved and supplemented, the present invention also comprises following technical characterictic.
Described organic carbon source is one or more the mixture in glucose, sucrose or starch, and it adds quality is the 7%-12% of iron lithium phosphate quality.
Described Li source compound is one or both mixtures in Quilonum Retard and lithium hydroxide.
Described Fe source compound is one or more in Ferrox, Iron diacetate, ferric oxide and iron nitrate.
In described wet ball grinding, solvent used is ethanol or acetone, and the quality of solvent is 1.5 times of pressed powder quality.
Described non-oxidizing atmosphere is nitrogen or argon gas.
Owing to adopting technical scheme of the present invention, in pre-ball milling step, choose polyphosphoric acid and primary ammonium phosphate and be as the object in compound phosphorus source: when the two mixes with lithium source, the easy generation monometallic that reacts with lithium source of primary ammonium phosphate, by product is water and ammonia.Polyphosphoric acid is met water can be hydrolyzed generation ortho-phosphoric acid, ortho-phosphoric acid further absorbing ammonia is so incensed that primary ammonium phosphate, thereby also participates in and the reacting of lithium source, therefore, appropriate polyphosphoric acid substitutes primary ammonium phosphate as phosphorus source, can reach the object that reduces water byproduct and ammonia in batch mixing system.Meanwhile, by ammonium salt and lithium source ball milling in advance, make the reaction of the two more abundant, what be conducive to monometallic generates synthetic with pure phase iron lithium phosphate completely.The technical program, processing ease, environmental pollution is few, can effectively improve the chemical property of LiFePO 4 material.
Accompanying drawing explanation
Fig. 1 be take the scanning electron microscope (SEM) photograph of the LiFePO 4 material that polyphosphoric acid and primary ammonium phosphate prepared as compound phosphorus source in the embodiment of the present invention 1.
Fig. 2 be the embodiment of the present invention 1 prepared take the LiFePO 4 material (a) that polyphosphoric acid and primary ammonium phosphate be compound phosphorus source, the LiFePO 4 material (b) that the polyphosphoric acid of take is phosphorus source, the LiFePO 4 material (c) that the primary ammonium phosphate of take is phosphorus source is assembled into the 0.2C discharge curve after button cell, wherein: rate of charge is 0.2C, charging/discharging voltage scope is 2.0-4.0V, and electrolytic solution is 1mol/L LiPF
6/ NSC 11801 (EC)+methylcarbonate (DMC) (volume ratio 1:1).
Fig. 3 be the embodiment of the present invention 1 prepared take the LiFePO 4 material (a) that polyphosphoric acid and primary ammonium phosphate be compound phosphorus source, the LiFePO 4 material (b) that the polyphosphoric acid of take is phosphorus source, the LiFePO 4 material (c) that the primary ammonium phosphate of take is phosphorus source is assembled into the cyclic curve figure that the 1C after button cell charges and discharge, charging/discharging voltage scope is 2.0-4.0V, and electrolytic solution is 1mol/L LiPF
6/ NSC 11801 (EC)+methylcarbonate (DMC) (volume ratio 1:1).
Embodiment
For better understanding the present invention, below in conjunction with drawings and Examples, the invention will be further described, but embodiments of the present invention are not limited to this.
Embodiment 1
Preparation process is as follows: by lithium hydroxide, primary ammonium phosphate and polyphosphoric acid, by lithium and phosphorus mol ratio, be that 1:1 weighs, the phosphorus mole number that primary ammonium phosphate provides accounts for 50% of phosphorus total mole number.According to the ethanol of the quality such as the quality of said mixture adds, ball milling mixes 1 hour, the monometallic slurry that obtains reacting completely; By the mol ratio of lithium, iron and phosphorus, be that 1:1:1 adds Ferrox again, by 10% of iron lithium phosphate quality, add glucose, secondary ball milling 4h is then dried at 70 ℃.Dried crushing material is placed in nitrogen atmosphere special atmosphere oven, with the heat-up rate of 2 ℃/min, is warming up to 400 ℃ and carries out presintering, be incubated 4 hours; Then with 2 ℃/min, be warming up to 750 ℃ again and calcine, be incubated 8 hours.With stove, naturally cool to room temperature, obtain LiFePO 4 material.In order relatively needing, also to have prepared respectively under the same conditions and take LiFePO 4 material and the LiFePO 4 material of polyphosphoric acid as phosphorus source of take that primary ammonium phosphate is phosphorus source.
LiFePO 4 material prepared by compound phosphorus source has carried out scanning electron microscope (SEM) research, its result as shown in Figure 1, powder body material by size comparatively the spherical particle of homogeneous form, primary particle size is between 200-400nm, less particle diameter contributes to improve the rate of migration of lithium ion in iron lithium phosphate body, and then improves the ionic conduction speed of material.
Usining primary ammonium phosphate and polyphosphoric acid makes cathode film as positive active material as the LiFePO 4 material in compound phosphorus source, cathode film by active substance, acetylene black and tetrafluoroethylene (solid content) in mass ratio 82:10:8 form; Using metal lithium sheet as negative pole; Barrier film is import microporous polypropylene membrane (Celgard 2400); Electrolytic solution is 1mol/L LiPF6/ NSC 11801 (EC)+methylcarbonate (DMC) (volume ratio 1:1), in the glove box of applying argon gas, is assembled into button cell.In order relatively to need, the LiFePO 4 material that primary ammonium phosphate (primary ammonium phosphate need separately pre-ball milling) is phosphorus source as the LiFePO 4 material in phosphorus source and the polyphosphoric acid of take of take of preparing under identical preparation condition is also assembled into button cell according to above-mentioned technique.Above battery is carried out to 0.2C charge-discharge test under room temperature, and LiFePO 4 material (c) that LiFePO 4 material (a), the LiFePO 4 material (b) that the polyphosphoric acid of take is phosphorus source and the primary ammonium phosphate of take that primary ammonium phosphate and polyphosphoric acid be compound phosphorus source the be phosphorus source first discharge specific capacity under 0.2C multiplying power of take is respectively 155.8mAh/g, 147.9mAh/g and 148.3mAh/g(as shown in Figure 2); As shown in Figure 3, above battery is carried out to 1.0 C charge-discharge tests under room temperature, LiFePO 4 material (c) that LiFePO 4 material (a), the LiFePO 4 material (b) that the polyphosphoric acid of take is phosphorus source and the primary ammonium phosphate of take that primary ammonium phosphate and polyphosphoric acid be compound phosphorus source the be phosphorus source first discharge specific capacity under 1.0 C multiplying powers of take is respectively 146.2mAh/g, 125.2mAh/g and 138.6mAh/g, charge and discharge circulation 50 times after, capability retention be respectively 99.6%, 97.6% and 96.6%(as shown in Figure 3).More than explanation selects appropriate polyphosphoric acid to replace primary ammonium phosphate, can effectively reduce the generation of water in batch mixing process, suppresses segregation, makes synthetic LiFePO 4 material purity higher, and the gram volume of material and cycle performance can effectively be improved; And using polyphosphoric acid as phosphorus source, due to polyphosphoric acid and primary ammonium phosphate reactive behavior lower, monometallic cannot complete reaction generates, and easily in sintering process, introduce impurity phase, so the gram volume of material is lower, cyclical stability is poor; Using primary ammonium phosphate as phosphorus source, and the water that by product brings, makes material easy segregation when drying, and the iron lithium phosphate crystalline phase that causes sintering to be prepared is impure, can suppress equally the performance of material gram volume and cycle performance.
Embodiment 2
By Quilonum Retard, primary ammonium phosphate and polyphosphoric acid, by lithium and phosphorus mol ratio, be that 1:1 weighs, the phosphorus mole number that primary ammonium phosphate provides accounts for 20% of phosphorus total mole number.According to the ethanol of the quality such as the quality of said mixture adds, ball milling mixes 1 hour, the monometallic slurry that obtains reacting completely; By the mol ratio of lithium, iron and phosphorus, be that 1:1:1 adds Iron diacetate again, by 8% of iron lithium phosphate quality, add glucose, secondary ball milling 4h is then dried at 70 ℃.Dried crushing material is placed in nitrogen atmosphere special atmosphere oven, with the heat-up rate of 2 ℃/min, is warming up to 500 ℃ and carries out presintering, be incubated 4 hours; Then with 2 ℃/min, be warming up to 700 ℃ again and calcine, be incubated 10 hours.With stove, naturally cool to room temperature, obtain LiFePO 4 material.Adopt LiFePO 4 material prepared by aforesaid method to make cathode film as positive active material, cathode film by active substance, acetylene black and tetrafluoroethylene (solid content) in mass ratio 82:10:8 form; Using metal lithium sheet as negative pole; Barrier film is import microporous polypropylene membrane (Celgard 2400); Electrolytic solution is 1mol/L LiPF6/ NSC 11801 (EC)+methylcarbonate (DMC) (volume ratio 1:1), in the glove box of applying argon gas, is assembled into button cell.The first discharge specific capacity of this material under 0.2C and 1.0C multiplying power is respectively 150.9mAh/g and 140.5mAh/g, with the specific storage after 1.0C multiplying power cycle charge-discharge 50 times, still kept the more than 98% of initial specific storage.
Embodiment 3
By Quilonum Retard, primary ammonium phosphate and polyphosphoric acid, by lithium and phosphorus mol ratio, be that 1:1 weighs, the phosphorus mole number that primary ammonium phosphate provides accounts for 80% of phosphorus total mole number.According to the ethanol of the quality such as the quality of said mixture adds, ball milling mixes 1 hour, the monometallic slurry that obtains reacting completely; By the mol ratio of lithium, iron and phosphorus, be that 1:1:1 adds ferric oxide again, by 12% of iron lithium phosphate quality, add glucose, secondary ball milling 4h is then dried at 70 ℃.Dried crushing material is placed in nitrogen atmosphere special atmosphere oven, with the heat-up rate of 2 ℃/min, is warming up to 500 ℃ and carries out presintering, be incubated 4 hours; Then with 2 ℃/min, be warming up to 800 ℃ again and calcine, be incubated 8 hours.With stove, naturally cool to room temperature, obtain LiFePO 4 material.Adopt LiFePO 4 material prepared by aforesaid method to make cathode film as positive active material, cathode film by active substance, acetylene black and tetrafluoroethylene (solid content) in mass ratio 82:10:8 form; Using metal lithium sheet as negative pole; Barrier film is import microporous polypropylene membrane (Celgard 2400); Electrolytic solution is 1mol/L LiPF6/ NSC 11801 (EC)+methylcarbonate (DMC) (volume ratio 1:1), in the glove box of applying argon gas, is assembled into button cell.The first discharge specific capacity of this material under 0.2C and 1.0C multiplying power is respectively 153.2mAh/g and 142.6mAh/g, with the specific storage after 1.0C multiplying power cycle charge-discharge 50 times, still kept the more than 98% of initial specific storage.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from spirit of the present invention and principle change, modification, substitute, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (6)
1. take the method that polyphosphoric acid and primary ammonium phosphate be compound phosphorus source synthesizing iron lithium phosphate material, its
Be characterised in that it comprises the following steps:
1) pre-ball milling step, is placed in ball grinder by polyphosphoric acid, primary ammonium phosphate and Li source compound, carries out wet ball grinding, and Ball-milling Time is 0.5-2h, makes monometallic complete reaction generation in advance; Wherein, polyphosphoric acid is pressed P
2o
5timing, the mol ratio of lithium and phosphorus is 1:1, the proportional range that the phosphorus mole number that primary ammonium phosphate provides accounts for the phosphorus mole number that compound phosphorus source provides is 10%-90%;
2) secondary ball milling step, in reaction in advance, generate in the ball grinder of monometallic, add in proportion Fe source compound and organic carbon source, continue ball milling 2-5h, then at 70 ℃, dry, wherein the mol ratio of lithium, iron and phosphate radical is 1:1:1, and the quality of organic carbon source is about the 7%-12% of iron lithium phosphate quality;
3) sintering step; the crushing material of drying is placed in atmosphere furnace; under non-oxidizing atmosphere protection; temperature rise rate with 2-5 ℃/min rises to 350-500 ℃ from room temperature; insulation 2-4h; with the temperature rise rate of 2-5 ℃/min, rise to roasting at 700-800 ℃ again, roasting time is 6-10h, thereby prepares LiFePO 4 material.
2. preparation method as claimed in claim 1, is characterized in that described organic carbon source is one or more the mixture in glucose, sucrose or starch.
3. preparation method as claimed in claim 1, is characterized in that described Li source compound is one or both mixtures in Quilonum Retard and lithium hydroxide.
4. preparation method as claimed in claim 1, is characterized in that described Fe source compound is one or more in Ferrox, Iron diacetate, ferric oxide and iron nitrate.
5. preparation method as claimed in claim 1, is characterized in that in described wet ball grinding, solvent used is ethanol or acetone, and the quality of solvent is 1.5 times of pressed powder quality.
6. preparation method as claimed in claim 1, is characterized in that described non-oxidizing atmosphere is nitrogen or argon gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310511418.4A CN103553016B (en) | 2013-10-25 | 2013-10-25 | A kind of lithium iron phosphate preparation method that is compound phosphorus source with polyphosphoric acid and primary ammonium phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310511418.4A CN103553016B (en) | 2013-10-25 | 2013-10-25 | A kind of lithium iron phosphate preparation method that is compound phosphorus source with polyphosphoric acid and primary ammonium phosphate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103553016A true CN103553016A (en) | 2014-02-05 |
| CN103553016B CN103553016B (en) | 2015-09-02 |
Family
ID=50007441
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310511418.4A Active CN103553016B (en) | 2013-10-25 | 2013-10-25 | A kind of lithium iron phosphate preparation method that is compound phosphorus source with polyphosphoric acid and primary ammonium phosphate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103553016B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101140985A (en) * | 2007-10-11 | 2008-03-12 | 河北工业大学 | Preparation method of lithium ionic cell positive pole material ferric phosphate lithium |
| CN101913590A (en) * | 2010-08-09 | 2010-12-15 | 中钢集团安徽天源科技股份有限公司 | Method for preparing iron-lithium phosphate by using high-purity magnet fine mineral powder as iron source |
| CN101941685A (en) * | 2009-07-09 | 2011-01-12 | 河南新飞科隆电源有限公司 | Preparation of spherical lithium iron phosphate material and lithium ion battery using spherical lithium iron phosphate material |
| CN101973539A (en) * | 2010-10-28 | 2011-02-16 | 浙江瑞邦科技有限公司 | Method for synthesizing lithium iron phosphate anode material at low cost |
-
2013
- 2013-10-25 CN CN201310511418.4A patent/CN103553016B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101140985A (en) * | 2007-10-11 | 2008-03-12 | 河北工业大学 | Preparation method of lithium ionic cell positive pole material ferric phosphate lithium |
| CN101941685A (en) * | 2009-07-09 | 2011-01-12 | 河南新飞科隆电源有限公司 | Preparation of spherical lithium iron phosphate material and lithium ion battery using spherical lithium iron phosphate material |
| CN101913590A (en) * | 2010-08-09 | 2010-12-15 | 中钢集团安徽天源科技股份有限公司 | Method for preparing iron-lithium phosphate by using high-purity magnet fine mineral powder as iron source |
| CN101973539A (en) * | 2010-10-28 | 2011-02-16 | 浙江瑞邦科技有限公司 | Method for synthesizing lithium iron phosphate anode material at low cost |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103553016B (en) | 2015-09-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107819115B (en) | Doped modified sodium vanadium fluorophosphate cathode material and preparation method thereof | |
| CN102201576B (en) | Porous carbon in situ composite lithium iron phosphate cathode material and preparation method thereof | |
| CN110061229B (en) | High-power-density long-cycle-life sodium ion battery positive electrode material and preparation method and application thereof | |
| CN102024951A (en) | Fluorinion-doped lithium iron phosphate material and preparation methods thereof | |
| CN101752562B (en) | Compound doped modified lithium ion battery anode material and preparation method thereof | |
| CN104617293B (en) | A kind of preparation method of the carbon coated lithium ferrous phosphate composite material of fluorine richness | |
| CN100418255C (en) | Method for preparing lithium enriched lithium ion phosphate powder | |
| CN103078113A (en) | Vanadium-titanium ion-codoped lithium iron phosphate material and preparation method thereof | |
| CN102583300A (en) | Fluorine and vanadium ion-doped lithium iron phosphate material and preparation method thereof | |
| CN107978738B (en) | Manganese sodium pyrophosphate/carbon composite cathode material and preparation and application thereof | |
| CN103904321A (en) | High-temperature solid-phase preparation method of lithium ion battery negative electrode material | |
| CN101931073B (en) | Preparation method of lithium iron phosphate/carbon composite cathode material | |
| CN104022282A (en) | High temperature solid state preparation method of lithium ion battery cathode material lithium metasilicate | |
| CN112133909A (en) | Antimony sulfide-based negative electrode material for lithium ion battery and preparation method thereof | |
| CN104241642A (en) | Lithium molybdate cathode material for lithium ion battery and preparation method thereof | |
| CN102931404A (en) | Phosphate potential boron-doped manganese phosphate lithium / carbon composite materials and preparation method thereof | |
| CN103050698A (en) | Vanadium lithium iron phosphate anode material and preparation method thereof | |
| CN100453454C (en) | Preparation method of lithium ferrous phosphate positive electrode material | |
| CN102299318B (en) | Preparation method of positive electrode material LiFePO4 for lithium ion battery | |
| CN108172813B (en) | Composite cathode material and preparation method thereof | |
| CN102394300A (en) | Preparation method of anode material lithium manganese phosphate of lithium ion battery | |
| CN102593447B (en) | A kind of metal-doped method of lithium iron phosphate positive material | |
| CN110021752B (en) | Lithium, aluminum and fluorine co-doped lithium iron phosphate cathode material and preparation method thereof | |
| CN101121510A (en) | Method for preparing Fe-position and P-position doping type lithium iron phosphate powder | |
| CN103682336A (en) | Method for improving conductivity of pure lithium iron phosphate anode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |